The relatively small dielectric Debye-like process of the monohydroxy alcohol 4-methyl-3-heptanol (4M3H) was found to depend slightly on the intramolecular conformation. Proton and deuteron nuclear magnetic resonance demonstrate that the hydroxyl dynamics and the overall molecular dynamics take place on similar time scales in contrast to the situation for the structural isomer 2-ethyl-1-hexanol (2E1H) [S. Schildmann et al., J. Chem. Phys. 135, 174511 (2011)]. This indicates a very weak decoupling of Debye-like and structural relaxation which was further probed using volume expansivity experiments. Shear viscosity as well as diffusometry measurements were performed and the data were analyzed in terms of the Debye-Stokes-Einstein equations. In mixtures of 4M3H with 2E1H the Debye-like process becomes much stronger and for 2E1H mole fraction of more than 25% the behavior of this alcohol is rapidly approached. This finding is interpreted to indicate that the ring-like supramolecular structures in 4M3H become energetically unfavorable when adding 2E1H, an alcohol that tends to form chain-like molecular aggregates. The concentration dependence of the Kirkwood factor in these mixtures displays a high degree of similarity with experimental results on monohydroxy alcohols in which the pressure or the location of the OH group within the molecular structure is varied.
Alkylacetamide-based model peptides display an intense Debye-type dielectric relaxation. In order to explore the extent to which this feature has to be regarded analogous to that in other supramolecular liquids, notably the monohydroxy alcohols, we applied broadband dielectric, time-dependent solvation, and near-infrared spectroscopies as well as shear rheology and various nuclear magnetic resonance techniques to mixtures of N-methylacetamide (NMA) or N-ethylacetamide (NEA) with N-methylformamide. Compared in the modulus format, dielectric relaxation, solvation dynamics, and mechanical response indicate a common global and local dynamics. The present spin-relaxation measurements reflect motional processes which are significantly faster than the dominant Debye dielectric response, and a similar conclusion is drawn from measurements of the shear viscosity. The NH overtone stretching vibrations reveal a temperature-dependent hydrogen-bond equilibrium that changes its characteristics near temperatures of 325 K. Finally, dielectric low-temperature data recorded for (NEA)0.4(NMF)0.6 mixed with 2-picoline indicate the existence of a critical concentration akin to the situation in various monohydroxy alcohol mixtures.
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